Organosiloxane and process for preparing the same

ABSTRACT

The present invention relates to an organosiloxane compound suitable for the modification of silicone rubbers and synthetic resins, an organosiloxane compound useful as its intermediate, and a process for preparing them. The organosiloxane compound of the present invention can be represented by the general formula (IV) ##STR1## wherein j is an integer of 1 to 2000, R is an alkyl group having 1 to 4 carbon atoms, and R 1  is a pentafluorophenyl group or a straight-chain or a branched fluoroalkyl group represented by the formula (II) 
     
         C.sub.a H.sub.b F.sub.2a-b+1                               (II) 
    
     wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a. 
     The siloxane compounds of the present invention also include compounds having siloxane chains, at least one of the chains having a substituent with a fluorine atom containing group at the terminal thereof. Each of the molecules constituting the polysiloxane compound of the present invention has a terminal hydrosilyl group portion and a fluorine atom-containing terminal substituent portion therein. Since the reactive group of the hydrosilyl group is chemically bonded to the synthetic resins, the deterioration in characteristics with time can be hindered. The synthetic resins can be provided with the specific function of the fluoroalkyl group without impairing characteristics which the polysiloxane has.

This application is a divisional of application Ser. No. 07/341,225,filed Apr. 21, 1989 now U.S. Pat. No. 4,992,521.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel organosiloxane compoundsuitable for the modification of silicone rubbers and synthetic resins,a novel organosiloxane compound useful as an intermediate, and a processfor preparing them.

2. Description of the Prior Art

Heretofore, a fluorine-containing group has been introduced intosilicone rubbers for the purpose of improving oil resistance and solventresistance. A typical example of the fluorine-containing group is a3,3,3-trifluoropropyl group, and the fluorine-containing group isusually introduced into a pendant site (branch site of a polysiloxanechain). Such fluorosilicone rubbers have been used singly and in theform of blends and copolymers of these rubbers and ordinary siliconerubbers.

Furthermore, siloxane resins have been used in synthetic resins with theintention of providing the synthetic resins with interfacialcharacteristics such as repellency, release properties and stainresistance as well as other characteristics such as heat resistancewhich siloxane compounds have. In these silicone resins, thestraight-chain polysiloxane compounds are mainly used. The polysiloxanecompound not having any group which is reactive with a synthetic resinis introduced into the synthetic resin by blending them, and thepolysiloxane compound having a group which is reactive with a grouppresent int eh synthetic resin is introduced thereinto by a chemicalbond. The polysiloxane compound can also be used as a raw material ofgraft polymers for the modification of the synthetic resin to which muchattention is paid of late, and particularly in this case, the so-calledone terminal-modified polysiloxane compound has been used in which oneterminal alone has a reactive group and another terminal is terminatedwith a trimethylsiloxy group.

The polysiloxane having the functional group only at the one terminalmay be prepared by hydrolyzing an organic dichlorosilane or utilizing anequilibrating reaction between a cyclosiloxane and a terminal terminatorwhich is a usual manufacturing process for the polysiloxane. However,this method has the drawbacks that it is hard to obtain the productshaving a narrow molecular distribution, and that it is difficult toattach the functional group only to the one terminal. In place of thismethod, another method (Japanese Patent Laid-open Publication Nos.78236/1984 and 275329/-1986) has been employed which comprises anionpolymerizing of a cyclosiloxane by the use of a trialkylsilanolatecompound of an alkaline metal as an initiator, and then reacting theresulting polymer with a trialkylchlorosilane having the desiredfunctional group so as to attach the functional group to the oneterminal thereof.

However, when the fluorine-containing substituent is introduced into thependant site as in conventional silicone rubbers, thefluorine-containing substituent is uniformly present in molded or coatedproducts, and therefore a great deal of the fluorine-containingsubstituent is required to obtain the expected effect. In addition,there are also troubles due to poor miscibility and a problem such asthe adverse influence of the substituents on other physical properties.

Also, when the siloxane compound not having any reactive group for thesynthetic resin is used for the purpose of improving the specificcharacteristics of the synthetic resin, the improvement depends upon thefunction of the polysiloxane. Thus, the degree of improvement to thesynthetic resin is insufficient in view of the fact that the demand ofthe specific characteristics is now increased. Moreover, in order toobtain the characteristics sought a great deal of the polysiloxanecompound is required, which leads to the problem that the other physicalproperties are adversely affected. The one terminal-modified siloxanecompound also has similar disadvantages,.because the other terminal ofthe molecular chain which has no reactive group for the synthetic resinis terminated with a trimethylsiloxy group. In addition, specificproperties such as oil repellency are scarcely improved by thedimethylsiloxane compound alone in which the other terminal isterminated with the trimethylsiloxy group. Also, in the case of acompound having a fluoroalkyl group in its molecule but not having anyreactive group for the synthetic resin in the molecule, the specificcharacteristics deteriorate notice-ably with time, and this kind ofcompound cannot sufficiently provide the resin with the characteristicssought and cannot conveniently be used in graft polymers.

In a conventional manufacturing process of the one terminal-modifiedsiloxane, a trialkylsilanolate is used as an initiator, and thus anadditional step is necessary in which a trialkylsilanol is reacted withan alkali metal compound to produce the trialkylsilanolate. In addition,this alkali metal compound (usually a lithium catalyst), which isexpensive, is used in an amount equivalent to the trialkylsilanol, andthe smaller the molecular weight of the polysiloxane product is and thegreater the production of the polysiloxane is, the greater the requiredamount of the catalyst is. In consequence, the cost of the preparedsiloxane compound is high, and for this reason, uses of the siloxanecompound are limited.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel siloxanecompound having a fluoroalkyl group at one molecular chain terminalthereof and a reactive group at the other molecular chain terminal inits one molecule, and another object of the present invention is toprovide a process for preparing this siloxane compound inexpensively.According to the present invention, the above-mentioned problems can besolved.

The present inventors have intensively conducted research to achieve theabove-mentioned objects, and they have prepared a compound representedby the following general formula (I); a siloxane compound obtained bymaking the compound as the intermediate having a fluorineatom-containing substituent at the α-position, the α-position orα'-position, or the α-position, α'-position or α"-position and having ahydrosilyl group at the ω-position; and a

process for preparing these compounds.

That is, the first feature of this invention is directed to a siloxanecompound represented by the general formula (I) ##STR2## wherein i is aninteger of 4 to 2000, and R¹ is a pentafluorophenyl group or asubstituent which is a straight-chain or a branched fluoroalkyl grouprepresented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-1                                 (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a.

The second feature of this invention is directed to a siloxane compoundrepresented by the general formula (I) regarding the first feature ofthis invention in which the substituent represented by R¹ is a3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctylgroup or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.

The third feature of this invention is directed to a process forpreparing a siloxane compound represented by the general formula (I)regarding the first invention which comprises the step of anionpolymerizing hexamethylcyclotrisiloxane using a trialkylsilanolrepresented by the general formula (III) ##STR3##

wherein R¹ is a pentafluorophenyl group or a substituent which is astraight-chain or a branched fluoroalkyl group represented by theformula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, asan initiator in the presence of a lithium catalyst in an amount of 0.05to 50 mole % based on the initiator in a polar solvent having no activehydrogen.

The fourth feature of this invention is directed to a siloxane compoundrepresented by the general formula (IV) ##STR4##

wherein j is an integer of 1 to 2000, R is an alkyl group having 1 to 4carbon atoms, and R¹ is a pentafluorophenyl group or a substituent whichis a straight-chain or a branched fluoroalkyl group represented by theformula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a.

The fifth feature of this invention is directed to a siloxane compoundrepresented by the general formula (IV) regarding the fourth feature ofthis invention in which the substituent represented by R¹ is a3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctylgroup or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.

The sixth feature of this invention is directed to a siloxane compoundrepresented by the general formula (V) ##STR5##

wherein each of k and l is an integer of 1 to 2000, R is an alkyl grouphaving 1 to 4 carbon atoms, and each of R² and R³ is an alkyl grouphaving 1 to 4 carbon atoms, a pentafluorophenyl group or a substituentwhich is a straight-chain or a branched fluoroalkyl group represented bythe formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R² and R³ is a fluorine atom-containing substituentother than the aforesaid alkyl group.

The seventh feature of this invention is directed to a siloxane compoundrepresented by the general formula (V) regarding the sixth feature ofthis invention in which the substituent represented by each of R² and R³is an alkyl group having 1 to 4 carbon atoms, a 3,3,3-trifluoropropylgroup, a tridecafluoro-1,1,2,2-tetrahydrooctyl group or aheptadecafluoro-1,1,2,2-tetrahydrodecyl group, and at least one of R²and R³ is a fluorine atom-containing substituent other than theaforesaid alkyl group.

The eighth feature of this invention is directed to a siloxane compoundrepresented by the general formula (VI) ##STR6##

wherein each of m, n and p is an integer of 1 to 2000, and a substituentrepresented by each of R⁴, R⁵ and R⁶ is an alkyl group having 1 to 4carbon atoms, a pentafluorophenyl group or a substituent which is astraight-chain or a branched fluoroalkyl group represented by theformula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R⁴, R⁵ and R⁶ is a fluorine atom-containing substituentother than the aforesaid alkyl group.

The ninth feature of this invention is directed to a siloxane compoundrepresented by the general formula (VI) regarding the eighth feature ofthis invention in which the substituent represented by each of R⁴, R⁵and R⁶ is an alkyl group having 1 to 4 carbon atoms, a3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctylgroup or a heptadecafluoro-1,1,2,2-tetrahydrodecyl group, and at leastone of R⁴, R⁵ and R⁶ is a fluorine atom-containing substituent otherthan the aforesaid alkyl group.

The tenth feature of this invention is directed to a process forpreparing a siloxane compound represented by the general formula (IV)regarding the fourth feature of this invention which comprises the stepof reacting a compound represented by the general formula (I') ##STR7##

wherein d is an integer of 1 to 2000 and R¹ is a pentafluorophenyl groupor a substituent which is a straight-chain or a branched fluoroalkylgroup represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,

with a chlorosilane represented by the general formula (VII) ##STR8##

wherein R is an alkyl group having 1 to 4 carbon atoms.

The eleventh feature of this invention is directed to a process forpreparing a siloxane compound represented by the general formula (V)regarding the sixth feature of this invention or a siloxane compoundrepresented by the general formula (VI) regarding the eighth feature ofthe subject invention which comprises the step of reacting a compound ora mixture of two or more compounds represented by the general formula(I') in the tenth feature of this invention, or a mixture of a compoundrepresented by the general formula (I') and one or more kinds ofcompounds represented by the general formula (VIII) ##STR9##

wherein q is an integer of 1 to 2000 and R⁷ is an alkyl group having 1to 4 carbon atoms, with a chlorosilane represented by the generalformula (IX) ##STR10##

wherein c is an interger of 2 or 3 and R is an alkyl group having 1 to 4carbon atoms.

The twelfth feature of this invention is directed to a process forpreparing a siloxane compound represented by the general formula (IV)regarding the fourth feature of this invention, a siloxane compoundrepresented by the general formula (V) regarding the sixth feature ofthis invention or a siloxane compound represented by the general formula(VI) regarding the eighth feature of this invention which comprises thesteps of anion polymerizing hexamethylcyclotrisiloxane using one kind ora mixture of two or more kinds of trialkylsilanols represented by thegeneral formula (III) in the third feature of this invention, or amixture of the trialkylsilanol represented by the general formula (III)and one or more kinds of trialkylsilanols represented by the generalformula (X) ##STR11##

wherein R⁸ is an alkyl group having 1 to 4 carbon atoms, as an initiatorin the presence of a lithium catalyst in an amount of 0.05 to 50 mole %based on the initiator in a polar solvent having no active hydrogen; andthen terminating the chain of the resulting polymer with a chlorosilanerepresented by the general formula (IX) ##STR12##

wherein g is an interger of 1 to 3 and R is an alkyl group having 1 to 4carbon atoms.

The thirteenth feature of this invention is directed t a process forpreparing a siloxane compound according to the third or the twelfthfeature of this invention wherein the lithium catalyst is metalliclithium, butyl lithium, lithium hydroxide, a lithium trialkylsilanolaterepresented by the general formula (XI) ##STR13##

wherein each of R⁹, R¹⁰ and R¹¹ is an alkyl group having 1 to 4 carbonatoms, a phenyl group, a pentafluorophenyl group, or a straight-chain ora branched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,

or a mixture of two or more thereof.

The fourteenth feature of this invention is directed to a process forpreparing a siloxane compound according to the third, the twelfth or thethirteenth feature of this invention wherein the amount of the lithiumcatalyst is in the range of 0.05 to 10 mole % based on thetrialkylsilanol which is the polymerization initiator.

The fifteenth feature of this invention is directed to a process forpreparing a siloxane compound according to the third, the twelfth, thethirteenth or the fourteenth feature of this invention wherein the polarsolvent having no active hydrogen is tetrahydrofuran, 1,4-dioxane,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,dimethylformamide, dimethyl sulfoxide or a mixture of two or morethereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a gel permeation chromatogram of siloxane compoundsprepared by the present invention.

FIG. 2 shows a gel permeation chromatogram of siloxane compoundsprepared by a conventional process.

FIG. 3 shows a gas chromatogram of the siloxane compounds represented bythe gel permeation chromatogram of FIG. 1.

FIG. 4 shows a gas chromatogram of the siloxane compounds represented bythe gel permeation chromatogram of FIG. 2.

DETAILED DESCRIPTION OF THE INVENTION

A compound represented by the general formula (I) regarding the firstfeature of this invention is characterized by having a terminal silanolgroup portion and a terminal substituent portion with a fluorine atomsimultaneously in one molecule thereof, as is apparent from the generalformula (I). This constitution is maintained even in the high-molecularweight polymer in which i of the general formula (I) has a high value,and each of the molecules constituting the polymer has the terminalsilanol group portion and the terminal substituent portion with thefluorine atom in the one molecule thereof. Additionally, the polymer ofthe present invention is characterized in that its dispersity is in apreferable case, from 1.1 to 1.2, which means that the distribution ofthe molecular weight is controlled very well.

The parameter i in the compound of the general formula (I) indicates thenumber of dimethylsiloxane units in a polydimethylsiloxanestraight-chain portion, and the value of i is preferably in the range of4 to 2000 so as to surely exert the specific function of thepolydimethylsiloxane when the compound (I) is introduced into a siliconerubber or a synthetic resin, to facilitate the introduction of thecompound (I) into the synthetic resin, and to facilitate the synthesisof the compound (I) itself. Furthermore, in the fluoroalkyl grouprepresented by the formula (II) regarding the first feature of thisinvention, the parameter a is preferably in the range of 3 to 18 for thesake of the easy availability of a raw material, the effective exertionof the function which the fluoroalkyl group has, and the ease ofsynthesis of the group (II).

When the compound of the present invention, either having or not havinga substituent, is introduced into the synthetic resin, the value of i inthe compound having the general formula (I) is preferably 700 or less,depending upon the kind and characteristics of the synthetic resin andthe desired function.

The compound represented by the general formula (I) regarding the firstfeature of this invention can be used as an intermediate at the time ofthe synthesis of the compound represented by the general formula (IV) ofthe fourth feature of this invention, the general formula (V) of thesixth feature of this invention or the general formula (VI) of theeighth feature of this invention. In addition, the compound representedby the general formula (I) regarding the first feature of this inventioncan be itself used as a siloxane compound which is useful for theimprovement of the specific characteristics of a synthetic resin such asa polyurethane or a polyester, and in this case, the hydroxyl grouppresent at one terminal of the molecule is reacted with the syntheticresin capable of reacting with the hydroxyl group, so that the compoundis incorporated therein by a chemical bond.

The siloxane compound represented by the general formula (IV) of thefourth feature of this invention, the general formula (V) of the sixthfeature of this invention or the general formula (VI) of the eighthfeature of this invention is characterized by having the terminalhydrosilyl group portion and the terminal substituent portion with afluorine atom simultaneously in one molecule thereof, as shown in eachgeneral formula. This constitution is maintained even in thehigh-molecular weight polymer in which j in the general formula (IV), kand l in the general formula (V), or m, n and p in the general formula(VI) have a high value, and each of the molecules constituting thepolymer has the terminal hydrosilyl group portion and the terminalsubstituent portion with the fluorine atom in the one molecule thereof.Additionally, the polymer of the present invention is characterized inthat its dispersity is in a preferable case, from 1.1 to 1.2, whichmeans that the distribution of the molecular weight is controlled verywell. Each parameter of j, k, l, m, n and p in the general formulae(IV), (V) and (VI) indicates the number of dimethylsiloxane units in apolydimethylsiloxane straight-chain portion, and the value of eachparameter is preferably in the range of 1 to 2000 so as to surely exertthe specific function of the polydimethylsiloxane when the compound ofthe present invention is introduced into a silicone rubber or asynthetic resin, to facilitate the introduction of the compound into thesynthetic resin, and to facilitate the synthesis of the compound itself.

When the compound, either having or not having a substituent, which isrepresented by each of the general formula (IV) regarding the fourthfeature of this invention, the general formula (V) regarding the sixthfeature of this invention and the general formula (VI) regarding theeighth feature of this invention, is introduced into the silicone rubberor the synthetic resin, each value of j, k, l, m, n and p in the generalformulae (IV), (V) and (VI) is most preferably 700 or less, dependingupon the kind, characteristics and a desired function of the siliconerubber or the synthetic resin.

Furthermore, in the fluoroalkyl group represented by the formula (II) inthe fourth, the sixth and the eighth features of this invention, theparameter a is preferably in the range of 3 to 18 for the sake of theeasy availability of a raw material, the effective exertion of thefunction which the fluoroalkyl group has, and the ease synthesis of thegroup (II).

The siloxane compound of the present invention is characterized by threekinds of structures. That is, the siloxane compound represented by thegeneral formula (IV) of the fourth invention has one siloxane chain, thecompound represented by the general formula (V) of the sixth feature ofthis invention has two siloxane chains, and the compound represented bythe general formula (VI) of the eighth feature of this invention hasthree siloxane chains on the basis of a hydrosilyl group. Therefore, theabove-mentioned structure of the siloxane compound can be optionallyselected in compliance with the kind and desired functional propertiesof silicone rubber or synthetic resin.

In the compound represented by the general formula (V) or (VI) of thesixth or the eighth feature of this invention, the respective siloxanechains preferably have the same chain length in most of the cases wherethe siloxane compound is used as a graft polymer to modify the siliconerubber or the synthetic resin. However, the siloxane compound can havedifferent molecular chain lengths in accordance with a particularpurpose. The substituents represented by R² and R³ in the generalformula (V) having the two molecular chains and the substituentsrepresented by R⁴, R⁵ and R⁶ in the general formula (VI) having thethree molecular chains may be different from each other. However, exceptthe case that it is necessary to provide the silicone rubber or thesynthetic resin with a specific function or except for the case that itis necessary to finely control the characteristics, the compoundpreferably has the same siloxane chain length and the same substituents,because if they are not the same, manufacturing steps increase and thetolerance of synthetic conditions is restricted.

The compound of the present invention represented by the general formula(IV) of the fourth feature of this invention, the general formula (V) ofthe sixth feature of this invention or the general formula (VI) of theeighth feature of this invention can be used as a raw material of amodifier for silicone rubbers which can be obtained by reacting thehydrosilyl group present in the molecule of the compound with anothersiloxane compound containing a vinyl group, and can be also used as amodifier for α-polyolefin synthetic resins capable of reacting with thehydrosilyl group present in the compound molecule of the presentinvention. The compound of the present invention can be used as anintermediate for a siloxane compound, because a substituent which isreactive with a desired synthetic resin can be introduced into thecompound of the present invention by a hydrosilyl-forming reaction,whereby new characteristics can be added to the desired synthetic resin.

The trialkylsilanol used as the initiator for the anion polymerizationwhich is represented by the general formula (III) of the third featureof this invention or the general formula (X) of the twelfth feature ofthis invention is easily available by hydrolyzing a trialkylchlorosilanehaving a desired alkyl group. Examples of the trialkylchlorosilaneinclude trimethylchlorosilane, ethyldimethylchlorosilane,n-butyldimethylchlorosilane, t-butyldimethylchlorosilane,isopropyldimethylchlorosilane, n-propyldimethylchlorosilane,pentafluorophenyldimethylchlorosilane,3,3,3-trifluoropropyldimethylchlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl) dimethylchlorosilane and(heptadecafluoro-1,1,2,2-tetrahydrodecyl) dimethylchlorosilane.

Examples of the lithium catalyst used in synthesizing the compound ofthe present invention include metallic lithium, butyl lithium, lithiumhydroxide and lithium trialkylsilanolates represented the followinggeneral formula (XI), and they can be used singly or as a mixture of twoor more thereof. ##STR14##

wherein each of R⁹, R¹⁰ and R¹¹ is an alkyl group having 1 to 4 carbonatoms, a phenyl group, a pentafluorophenyl group or a straight-chain ora branched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a.

Catalysts other than these lithium catalysts, for example, alkali metalcompounds such as sodium catalysts and potassium catalysts are alsousable, but when this a kind of catalyst is used to form the desiredsiloxane compound represented by the general formula (I) of the firstfeature of this invention, the general formula (IV) of the fourthfeature of this invention, the general formula (V) of the sixth featureof this invention or the general formula (VI) of the eighth feature ofthis invention, the yield of the product is low. In consequence, thecatalysts other than the lithium catalysts are improper in the synthesisof the compound regarding the present invention.

The amount of the catalyst is preferably in the range of 0.05 to 50 mole%, more preferably 0.05 to 10 mole %, based on the trialkylsilanol whichis the polymerization initiator. When the amount of the catalyst is lessthan the lower limit of 0.05 mole %, the rate of the polymerization istoo low and impractical. The upper limit of the amount of the catalystis 50 mole % or less, preferably 10 mole % or less, when a small amountof the catalyst is used in the synthesis on a small scale and in theproduction of the compound having a high molecular weight, i.e., when itis difficult to precisely measure the catalyst. Even if the amount ofthe catalyst is in excess of 50 mole %, a higher effect cannot beexpected, and the use of the dangerous catalyst in an amount beyond thenecessary level leads to a decrease in safety, a drop in manufacturingefficiency and a rise of manufacturing cost inconveniently.

When the polysiloxane compound is synthesized by living polymerizationunder conditions in which the lithium catalyst is used in an amount of50 mole % or less, based on the trialkylsilanol which is thepolymerization initiator, in accordance with a preparation process ofthe present invention, the thus synthesized polysiloxane compound hasthe feature that the polymer is densely constituted of the moleculeseach containing dimethylsiloxane units the number of which can vary oneby one. In the polysiloxane compound synthesized by the conventionalprocess, the polymer is constituted of the molecules containing siloxaneunits of the cyclic siloxane which is a raw material, and the number ofthe silioxane units varies by several. For example, whenhexamethylcyclotrisiloxane having three siloxane units is used as theraw material, most of the molecules constituting the obtained polymercontain siloxane units, the number of which varies by three. This can beeasily confirmed by gas chromatography, liquid chromatography (gelpermeation chromatography) or the like. FIGS. 1 and 2 show gelpermeation chromatograms of siloxane compounds having a molecular weightof 1,000 which were synthesized by the preparation process of thepresent invention (the lithium catalyst was used in an amount of 1.0mole % based on the trialkylsilanol) and the conventional manufacturingprocess (the trialkylsilanol and the lithium catalyst were each used inan equimolar amount) under the same conditions except for the amounts ofthe catalysts. FIGS. 3 and 4 are the gas chromatograms of the compoundswhich correspond to those of FIGS. 1 and 2. Peaks 1 to 5 in FIGS. 3 and4 correspond to the following compounds: ##STR15##

In FIG. 1 showing the chart of the compound invention, one definite peakis present, because the polymer is composed of one by one siloxane unitand is not separated by the gel permeation chromatography. On thecontrary, in FIG. 2 showing the chart of the compound synthesized by theconventional process, a plurality of peaks are present. Furthermore, incontrast to the chart of the compound synthesized by the preparationprocess of the present invention, FIG. 3, the chart concerning thecompound obtained by the conventional process, FIG. 4 indicates thattall peaks of the siloxane units are present in every third place. Thiselucidates that as the amount of the lithium decreases from theequivalent amount of the trialkylsilanol, a ratio of two short peaksbetween the tall peaks to the latter tall peaks in FIG. 4 changes fromthe peak distribution of FIG. 4 in which the two short peaks are presentbetween the tall peaks, to that of FIG. 3 in which the peakscorresponding to the two short peaks in FIG. 4 are tall.

In principle, gas chromatography cannot analyze samples which do notgasify at a certain temperature. Therefore, the greater the molecularweight of the polymer is, the harder the gasification is, and in FIGS. 3and 4, the height of the peaks on the low-molecular side is notproportional to that of the peaks on the high-molecular side (the peakson the right side of FIGS. 3 and 4 denote the polymers having highermolecular weights), and therefore the peaks shown in FIGS. 3 and 4 donot always indicate a quantitative ratio of the polymers. Accordingly,it is impossible to determine the distribution of molecular weight fromthe gas chromatograms of FIGS. 3 and 4. The molecular weightdistributions of the polymers are indicated by the gel permeationchromatograms (FIGS. 1 and 2).

Suitable examples of polar solvent not having any active hydrogen whichis used in the synthesis of the present invention includetetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethyleneglycol dimethyl ether, dimethylformamide and dimethyl sulfoxide, andthey may be used singly or in combination. Above all, tetrahydrofuran isparticularly preferable. When a solvent having active hydrogen is used,the reaction is hindered, and when a non-polar solvent is used, thereaction scarcely proceeds. Therefore, the employment of these kinds ofsolvents is not preferable.

Reaction temperature is preferably in the range of 0° to 50° C., morepreferably 15° to 25° C. When the reaction temperature is less than 0°C., the rate of the polymerization is low and impractical; when it ismore than 50° C., the molecular weight distribution of the producedpolysiloxane is too high.

Reaction time depends upon the reaction temperature, and it is preferredthat the reaction be brought to an end when about 95% ofhexamethylcyclotrisiloxane has been consumed. In the case that thereaction temperature is in the range of 15° to 20° C. and the reactiontime is suitably in the range of 10 to 20 hours. The unnecessarilyprolonged reaction time is not preferable, since the molecular weightdistribution expands.

The molecular weight of the polysiloxane can be easily controlled byadjusting amounts of the trialkylsilanol, which is the initiator, andhexamethylcyclotrisiloxane, in the case that the number of thedimethylsiloxane units is 2000 or less (number average molecularweight=about 150000 or less). In addition, when the number averagemolecular weight is greater, the control of the molecular weight can beaccomplished by changing conditions for living polymerization.

As described above, number of the siloxane chains on the basis of thehydrosilyl group, is one in the general formula (IV) of the fourthfeature of this invention, two in the general formula (V) of the sixthfeature of this invention, and three in the general formula (VI) of theeighth feature of this invention, but the number of chains can becontrolled by adjusting the number of chlorine atoms bonded to a siliconatom in the chlorosilane used which is represented by the generalformula (IX) ##STR16##

wherein g is an interger of 1 to 3 and R is an alkyl group having 1 to 4carbon atoms.

Incidentally, the aforesaid chlorosilane is what is used as a chainterminator after the trialkylsilanol has been anion polymerized.

When dialkylchlorosilane, in which the number of the chlorine atoms inthe general formula (IX) is one, is used as the chain terminator, theobtained compound has one siloxane chain on the basis of the hydrosilylgroup, as shown in the general formula (IV) of the fourth feature of theinvention. When alkyldichlorosilane, in which the number of the chlorineatom in the general formula (IX) is two, is used as the chainterminator, the obtained compound has two siloxane chains on the basisof the hydrosilyl group, as shown in the general formula (V) of thesixth feature of this invention. Furthermore, when trichlorosilane, inwhich the number of the chlorine atom in the general formula (IX) isthree, is used as the chain terminator, the obtained compound has threesiloxane chains on the basis of the hydrosilyl group, as shown in thegeneral formula (VI) of the eighth feature of this invention.

Alternatively, the compounds represented by the general formula (IV) ofthe fourth feature of this invention, the general formula (V) of thesixth feature of this invention and the general formula (VI) of theeighth feature of this invention can be rapidly and easily obtained inthe following manner: Several intermediates having different molecularweights and having fluorine substituents at the terminals thereof arepreviously prepared in the form of a terminal silanol represented by thegeneral formula (I') used in the tenth feature of this invention, and achlorosilane corresponding to the desired number of siloxane chains isreacted with the previously prepared intermediate, as in the tenth andthe eleventh features of this invention. This is the greatest feature ofthe preparation process regarding the present invention.

Furthermore, when a chlorine catching compound is used in theabove-mentioned reaction with the chlorosilane, this reaction canproceed more smoothly.

The siloxane compound having two or three siloxane chains, on the basisof the hydrosilyl group, in which the length and the terminalsubstituents of the siloxane chains are different can be synthesized inthe following manner: Compounds having the desired two or moresubstituents and the desired siloxane chain length are separatelyproduced by the anion polymerization at a desired ratio, and thenunified, and chain termination is made by the use of analkyldichlorosilane or trichlorosilane. When the siloxane compoundhaving the same chain length and the two or more different substituentsis synthesized, a mixture of two or more kinds of trialkylsilanols,which are initiators, in a desired ratio is used as an initiator in theanion polymerization, and the chain of the polymer is then terminatedwith the alkyldichlorosilane or trichlorosilane.

Now, reference will be made briefly to the process for preparing thecompound of the present invention.

In the first place, (tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol (XII) and hexamethylcyclotrisiloxane (XIII)are subjected to ring opening living polymerization in the presence of abutyl lithium catalyst, and afterward dimethylchlorosilane is addedthereto as a chain terminator, thereby obtaining a polysiloxane compoundhaving a desired average polymerization degree represented by theundermentioned formula (XVI).

Furthermore, compound (XIV) obtained in the above-mentioned process, istreated with a weak acid such as acetic acid or calcareous water at roomtemperature so as to effect chain termination, whereby a compoundrepresented by the undermentioned formula (XV) is obtained in which oneterminal group of its molecular chain is a silanol. If the compound (XV)is substituted for the compound (XIV), a compound represented by theformula (XVI) can be prepared. ##STR17##

wherein Bu is a butyl group, X¹ is a hydrogen atom or a lithium atom, eis an integer of 1 to 1999, and f is an integer of 0 to 1999.

For the compound represented by the formula (XII(), (XIV) or (XV) in thepreparation process, methyldichlorosilane can be used in place ofdimethylchlorosilane as the chain terminator, so that a polysiloxanecompound represented by the formula (XVII) is obtained which has twosiloxane chains on the basis of the hydrosilyl group. ##STR18##

wherein X¹ is a hydrogen atom or a lithium atom, and f is an integer of0 to 1999.

For the compound represented by the formula (XII), (XIV) or (XV) in thepreparation process, trichlorosilane can be used as the chainterminator, so that a polysiloxane compound represented by the formula(XVIII) is easily obtained which has three siloxane chains on the basisof the hydrosilyl group. ##STR19##

wherein X¹ is a hydrogen atom or a lithium atom, and f is an integer of0 to 1999.

According to each process just described, the novel siloxane compoundhaving the fluorine atom containing group at the α-position, theα-position or α'-position, or the α-position, α'-position or α"-positionand having the hydrosilyl group at the ω-position can be prepared easilyand inexpensively.

When the compound having a silanol group at the molecular chain terminalthereof according to the present invention is reacted with a syntheticresin such as a polyurethane or a polyester capable of reacting withthis compound in order to incorporate it in the resin via a chemicalbond, the following functional effects can be obtained.

(1) Since the reactive group in the compound of the present invention ischemically bonded to the polyurethane or the polyester, the syntheticresin incorporated with the compound of the present invention caninhibit the deterioration in characteristics with time.

(2) Since a fluoroalkyl group is present together with adimethylsiloxane chain in one molecule, it is possible to provide thesynthetic resin with various excellent specific functions of thefluorine atom-containing substituent, such as water repellency, stainresistance, release properties, non-adhesive properties, oil-repellentproperties, low frictional properties and snow deposition resistance,which cannot be obtained from and is superior to a conventionalpolysiloxane terminated with a trimethyl siloxy group, without impairingthe characteristics of the polysiloxane.

(3) It is possible to obtain a very narrow molecular weight distribution(dispersity) of 1.1 to 1.2, and therefore, when the compound of thepresent invention having a uniform molecular chain length is introducedinto a synthetic resin, the latter can take a more uniform structurethan when a compound having an non-uniform molecular chain length isused. In addition, the synthetic process of the present invention by theutilization of living polymerization does not form any cyclic compoundsof dimethylsiloxane which cannot be removed by any means, though aconventional equilibrating reaction using an acidic or basic catalystcannot avoid the production of the cyclic compound. Accordingly, thedeterioration in physical properties and bleeding of the modifiedsynthetic resins and scatter of product quality, which are attributableto these cyclic compounds, can be inhibited, so that the physicalproperties and the like can be improved.

(4) Also when the compound of the present invention is used as a graftpolymer so as to improve characteristics of a synthetic resin, such aswater repellency, stain resistance, release properties, non-adhesiveproperties, oil-repellent properties and low frictional properties, thesynthetic resin can be provided with not only the function of thesiloxane but also the specific function of the fluoro-alkyl group.Furthermore, since the compound of the present invention is able to havea uniform molecular chain length, in that case the uniform structure canbe obtained, and in addition the molecular chain lengths of the siloxaneportion and the fluoroalkyl group portion can be changed so as toregulate the characteristics. In consequence, the compounds of thepresent invention can be applied to uses in which high performance isrequired, and in particular, it can be applied to the surfacemodification of a synthetic resin, to which uses the conventionaldimethylsiloxane having no fluoroalkyl group cannot be applied. When thecompounds of the present invention, having the hydrosilyl group at theterminal of the molecular chain, are used to improve the characteristicsof molded products and coated products of silicone rubbers, the densityof fluoralkyl groups are increased at the surface portions of theseproducts as compared to the interiors thereof, because the fluoroalkylgroup is present at the longest distance from the reactive group capableof chemically bonding to the silicone rubber or the like, and the degreeof freedom of the fluoroalkly group is higher than when the fluoroalkylgroup is present on the pendant site. To sum up, the compounds of thepresent invention can obtain a great improvement in surfacecharacteristics under the influence of a small amount of the fluoroalkylgroup in contrast to conventional compounds in which the fluoroalkylgroup exists only in the pendant portion, and the molecular chain lengthof the compounds according to the present invention can be altered so asto control the characteristics. Moreover, siloxane compounds havingfluoroalkyl groups with more fluorine atoms can be synthesized moreeasily than compounds having the group in the pendant site, and when thefluoroalkyl groups are introduced into both the pendant portion and themolecular chain terminal, the silicone rubber possesses improved oilresistance and solvent resistance.

Since the compound of the present invention is able to have a verynarrow molecular weight distribution (dispersity) of 1.1 to 1.2, whenthe compound is introduced into the synthetic resin, the latter can takea more uniform structure than when a compound having a non-uniformmolecular chain length is used. In addition, the synthetic process ofthe present invention by the utilization of living polymerization doesnot form any cyclic compounds of dimethylsiloxane which cannot beremoved by any means, though an equilibrating reaction using an acidicor basic catalyst cannot avoid the production of cyclic compounds.Accordingly, the deterioration in physical properties and bleeding ofthe modified synthetic resins and scatter of product quality, which areattributable to these cyclic compounds, can be inhibited, so that thephysical properties and the like can be improved.

When the compounds of the present invention, having the hydrosilyl groupat the terminal thereof, are introduced into an α-polyolefin syntheticresin, and when in place of a conventional one terminal-modifiedpolysiloxane compound not having any reactive group and fluoroalkylgroup in one molecule, the compound of the present invention having thehydrosilyl group portion, to which the reactive group capable of bondingto the desired synthetic resin has been added by a hydrosilyl-formingtreatment, is introduced into the synthetic resin so as to improve thespecific characteristics of the resin, the following effects can beobtained.

(1) Since the reactive group in the compound of the present invention ischemically bonded to the synthetic resin, the synthetic resinincorporated with the compound of the present invention can inhibit thedeterioration in characteristics with time.

(2) Since the fluoroalkyl group is present together with thedimethylsiloxane chain in one molecule, it is possible to provide thesynthetic resin with various excellent specific functions of thefluorine atom-containing substituent such as water repellency, stainresistance, release properties, non-adhesive properties, oil-repellentproperties, low frictional properties and snow deposition resistance,which cannot be obtained from and is superior to the conventionalpolysiloxane terminated with trimethyl siloxy group without impairingthe characteristics of the polysiloxane.

(3) It is possible to obtain a very narrow molecular weight distribution(dispersity) of 1.1 to 1.2, and therefore, when the compound of thepresent invention having a uniform molecular chain length is introducedinto the synthetic resin, the latter can take a more uniform structurethan when a compound having an non-uniformed molecular chain length isused. In addition, the synthetic process of the present invention, bythe utilization of living polymerization does not form any cycliccompounds of dimethylsiloxane which cannot be removed by any means,though a conventional equilibrating reaction using an acidic or basiccatalyst cannot avoid the production of the cyclic compounds.Accordingly, the deterioration in physical properties and bleeding ofthe modified synthetic resins and scatter of product quality, which areattributable to these cyclic compounds, can be inhibited, so that thephysical properties and the like can be improved.

(4) Also when the compound of the present invention is used as a graftpolymer so as to improve characteristics of a synthetic resin such aswater repellency, stain resistance, release properties, non-adhesiveproperties, oil-repellent properties and low frictional properties, thesynthetic resin can be provided with not only the function of thesiloxane but also the specific function of the fluoroalkyl group.Furthermore, since the compounds of the present invention are able tohave a uniform molecular chain length, in that case, the uniformstructure can be obtained, and in addition the molecular chain lengthsof the siloxane portion and the fluoroalkyl group portion can be changedso as to regulate the characteristics. In consequence, the compound ofthe present invention can be applied to uses in which high performanceis required, and in particular, it can be applied to the surfacemodification of the synthetic resin, to which uses the conventionaldimethylsiloxane having no fluoroalkyl group cannot be applied.

(5) In the compounds of the present invention, three conditions can beoptionally selected, which are the number of 1 to 3 siloxane chains onthe basis of the hydrosilyl group which is reactive to the syntheticresin, the length of the siloxane chains, and the kind of fluorineatom-containing substituent at the terminal of the siloxane chain. Whenthe compound of the present invention having the three requiredconditions is introduced into the desired synthetic resin or siliconerubber, finely controlled functions and characteristics can be given tothe resin or the like.

Moreover, when the compound of the present invention is synthesized inaccordance with the process of the present invention, the followingeffects can be obtained.

(1) Since the amount of the expensive lithium catalyst in the presentinvention is 1/2 to 1/200 of the necessary amount in the conventionalprocess, the siloxane compound having a low molecular weight can bemanufactured at low cost, though the conventional process requires agreat deal of the catalyst to manufacture such a kind of siloxanecompound. Accordingly, the process of the present invention permitsapplying low-molecular polysiloxane compounds to uses in which expensivesiloxane compounds have not been accepted from an economical viewpoint.In addition, a smaller amount of metallic lithium or an alkyllithiumcompound, which is dangerous is handled, and thus safety is improved.

(2) In the process of the present invention, a trialkylsilanol can beused as a polymerization initiator. Therefore, the step of previouslypreparing lithium trialkylsilanolate, which the conventional processrequires, is not necessary any more, with the result that equipmentinvestment can be decreased, which permits a supply of inexpensiveproducts.

(3) The polysiloxane compound synthesized by the process of the presentinvention is densely composed of molecules containing dimethylsiloxaneunits which increase one by one, and therefore, when the polysiloxanecompound of the present invention is used to provide the synthesizedresin or silicone rubber with necessary functions, the compound can bemore uniformly incorporated in the synthetic resin or the siliconerubber than a conventional polymer composed of molecules each containingrepeating units which vary three by three, whereby the characteristicsof the resin or the rubber can be improved.

The drawings attached hereto have been described hereinbefore, but theycan be summarized as follows:

FIGS. 1 and 2 show gel permeation chromatograms of siloxane compoundshaving a molecular weight of 1000 which were synthesized by thepreparation process of the present invention (the lithium catalyst wasused in an amount of 1.0 mol % based on a trialkylsilanol) and aconventional manufacturing process (the trialkylsilanol and the lithiumcatalyst were each used in an equimolar amount) under the sameconditions except for amounts of the catalysts.

FIGS. 3 and 4 are chromatograms of compounds which correspond to thoseof FIGS. 1 and 2.

Peaks 1 to 5 in FIGS. 3 and 4 correspond to the following compounds:##STR20##

EXAMPLES

Now, the present invention will be described in detail with reference toexamples, but the scope of the present invention should not be limitedto these examples.

EXAMPLE 1

Preparation of1-(tridecafluoro-1,1,2,2-tetrahydrooctyl)-9-hydrodecamethylpentasiloxane:

To a 1-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 100 ml of previously dried tetrahydrofuran,100.0 g (0.238 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 52.9 g (0.238mole) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.79 ml (1.5mole/l) of a butyl lithium hexane solution was then added thereto andpolymerization was performed at 20° C. for 10 hours.

Next, 24.7 g (0.261 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separating funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 100 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of ¹ H-NMR spectrum, IR spectrum and GPC (gelpermeation chromatography) as well as quantitative data of an Si-H groupwere as follows, and it was confirmed that the obtained siloxanecompound had the following structure: ##STR21##

¹ H-NMR(CDCl₃): δppm 0.18 (Si(CH₃)₂, s, 30H) 0.53-2.80 (SiCH₂ CH₂,broad, 4H) 4.55 (Si-H, m, 1H)

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                    850                                                 Weight average molecular weight (Mw)                                                                    930                                                 Dispersity (Mw/Mn)        1.1                                                 (molecular weight on calculated values was 702)                               Quantitative data of Si--H group:                                             H (ppm)                   1442   (ppm)                                        Molecular weight calculated on H (ppm)                                                                  693                                                 ______________________________________                                    

EXAMPLE 2

Preparation of a dimethylpolysiloxane having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position and ahydrosilyl group at the ω-position:

To a 2-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 400 ml of previously dried tetrahydrofuran,5.0 g (0.0119 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 50.5 g (1.57moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.040 ml(1.5 moles/l) of hexane solution of butyl lithium was then added theretoand polymerization was performed at 20° C. for 15 hours.

Next, 1.24 g (0.0131 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separation funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 32660                                                  Weight average molecular weight (Mw)                                                                 35930                                                  Dispersity (Mw/Mn)     1.1                                                    Quantitative data of Si--H group:                                             H (ppm)                32.1     (ppm)                                         Molecular weight calculated on H (ppm)                                                               31153                                                  Viscosity (25° C.):                                                    1385 centipoise                                                               ______________________________________                                    

EXAMPLE 3

Preparation of a dimethylpolysiloxane having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position and ahydrosilyl group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 2000 ml of previously dried tetrahydrofuran,12.0 g (0.0285 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 1981.1 g(8.90 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.095ml (1.5 moles/l) of a butyl lithium hexane solution was then addedthereto and polymerization was performed at 20° C. for 20 hours.

Next, 2.97 g (0.0313 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 63410                                                  Weight average molecular weight (Mw)                                                                 75930                                                  Dispersity (Mw/Mn)     1.2                                                    Quantitative data of Si--H group:                                             H (ppm)                15.1     (ppm)                                         Molecular weight calculated on H (ppm)                                                               66225                                                  Viscosity (25° C.):                                                    3538 centipoise                                                               ______________________________________                                    

EXAMPLE 4

Preparation of a dimethylpolysiloxane having aheptadecafluoro-1,1,2,2-tetrahydrodecyl group at the α-position and ahydrosilyl group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 2000 ml of previously dried tetrahydrofuran,100.0 g (0.1915 mole) of(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylsilanol and 1803.6 g(8.10 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.64ml (1.5 moles/l) of a butyl lithium hexane solution was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 19.9 g (0.211 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 11710                                                  Weight average molecular weight (Mw)                                                                 12896                                                  Dispersity (Mw/Mn)     1.1                                                    Quantitative data of Si--H group:                                             H (ppm)                103.3    (ppm)                                         Molecular weight calculated on H (ppm)                                                               9680                                                   Viscosity (25° C.):                                                    147 centipoise                                                                ______________________________________                                    

EXAMPLE 5

Preparation of a dimethylpolysiloxane having a 3,3,3-trifluoropropylgroup at the α-position and a hydrosilyl group at the ω-position:

To a 2-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 800 ml of previously dried tetrahydrofuran,10.0 g (0.581 mole) of (3,3,3-trifluoropropyl)dimethylsilanol and 567.2g (2.55 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.19ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 6.04 g (0.0639 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 9520                                                   Weight average molecular weight (Mw)                                                                 10490                                                  Dispersity (Mw/Mn)     1.1                                                    Quantitative data of Si--H group:                                             H (ppm)                112.5    (ppm)                                         Molecular weight calculated on H (ppm)                                                               8890                                                   Viscosity (25° C.):                                                    116 centipoise                                                                ______________________________________                                    

EXAMPLE 6

Preparation of a dimethylpolysiloxane having a pentafluorophenyl groupat the α-position and a hydrosilyl group at the ω-position:

To a 1-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 100 ml of previously dried tetrahydrofuran,10.0 g (0.04127 mole) of pentafluorophenyldimethylsilanol and 194.0 g(0.138 mole) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.14ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 4.29 g (0.0454 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 29760 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1120-1050cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                   5807                                                 Weight average molecular weight (Mw)                                                                   6370                                                 Dispersity (Mw/Mn)       1.1                                                  Quantitative data of Si--H group:                                             H (ppm)                  203.3  (ppm)                                         Molecular weight calculated on H (ppm)                                                                 4920                                                 Viscosity (25° C.):                                                    64 centipoise                                                                 ______________________________________                                    

EXAMPLE 7

Preparation of a dimethylpolysiloxane having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position and asilanol group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 1000 ml of previously dried tetrahydrofuran,50.0 g (0.119 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 1130.2 g(5.08 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.40ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed t 20° C. for 15 hours.

Next, acetic acid was further added thereto, followed by stirring for 1hours. The thus synthesized material was then transferred into aseparation funnel, then washed with water, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 3200-3400 cm⁻¹ (Si-OH() 2970 cm⁻¹ (C-H) 1260 cm⁻¹ (Si-CH₃)1250-1150 cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                  10850                                                 Weight average molecular weight (Mw)                                                                  12020                                                 Dispersity (Mw/Mn)      1.1                                                   Quantitative data of OH group:                                                OH (wt %)               0.18    (wt %)                                        Molecular weight calculated on OH (wt %)                                                              9444                                                  Viscosity (25° C.):                                                    154 centipoise                                                                ______________________________________                                    

EXAMPLE 8

Preparation of a dimethylpolysiloxane having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position and ahydrosilyl group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 1000 ml of previously dried tetrahydrofuran,50.0 g (0.119 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 1130.2 g(5.08 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.40ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 12.35 g (0.1306 mole) of dimethylchlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows:

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 11910                                                  Weight average molecular weight (Mw)                                                                 12850                                                  Dispersity (Mw/Mn)     1.1                                                    Quantitative data of Si--H group:                                             H (ppm)                101.6    (ppm)                                         Molecular weight calculated on H (ppm)                                                               9843                                                   Viscosity (25° C.):                                                    165 centipoise                                                                ______________________________________                                    

EXAMPLE 9

Preparation of a dimethylpolysiloxane (the number of siloxane chains onthe basis of a hydrosilyl group was 2) having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position andα'-position and a hydrosilyl group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 1000 ml of previously dried tetrahydrofuran,50.0 g (0.119 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 1130.2 g(5.08 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.04ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 7.51 g (0.0653 mole) of methyldichlorosilane was further addedthereto, followed by stirring for 1 hour in order to bring thepolymerization to an end. The thus synthesized material was thentransferred into a separatory funnel, then washed with water to removethe resulting lithium chloride therefrom, and dried with anhydroussodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows. Furthermore, it was confirmed that the obtained siloxanecompound had two siloxane chains on the basis of the hydrosilyl group inwhich s and t in the following formula had about the same value, judgingfrom the fact that molecular weights obtained from the GPC data and H(ppm) were about twice as much as those in Example 8 (the number ofsiloxane chains on the basis of a hydrosilyl group was 1) in which thesame conditions as in this example were repeated on the identical scalewith the exception that only the kind of chlorosilane was changed.##STR22##

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 19740                                                  Weight average molecular weight (Mw)                                                                 23720                                                  Dispersity (Mw/Mn)     1.2                                                    Quantitative data of Si--H group:                                             H (ppm)                53.9     (ppm)                                         Molecular weight calculated on H (ppm)                                                               18550                                                  Viscosity (25° C.):                                                    423 centipoise                                                                ______________________________________                                    

EXAMPLE 10

Preparation of a dimethylpolysiloxane (the number of siloxane chains onthe basis of a hydrosilyl group was 3) having atridecafluoro-1,1,2,2-tetrahydrooctyl group at the α-position,α'-position and α"-position and a hydrosilyl group at the ω-position:

To a 5-liter three-necked round bottom flask equipped with a stirrer anda cooling device were fed 1000 ml of previously dried tetrahydrofuran,50.0 g (0.119 mole) of(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilanol and 1130.2 g(5.08 moles) of hexamethylcyclotrisiloxane with an N₂ stream, and 0.40ml (1.5 moles/l) of a hexane solution of butyl lithium was then addedthereto and polymerization was performed at 20° C. for 15 hours.

Next, 5.90 g (0.0435 mole) of trichlorosilane was further added thereto,followed by stirring for 1 hour in order to bring the polymerization toan end. The thus synthesized material was then transferred into aseparatory funnel, then washed with water to remove the resultinglithium chloride therefrom, and dried with anhydrous sodium sulfate.

Afterward, low-boiling substances in the resulting reaction product weredistilled off under conditions of 100° C. and 10 mmHg over 2 hours,thereby obtaining the desired siloxane compound in a substantiallyquantitative yield. With regard to the thus obtained siloxane compound,analytical results of IR spectrum, GPC (gel permeation chromatography)and viscosity as well as quantitative data of an Si-H group were asfollows. Furthermore, it was confirmed that the obtained siloxanecompound had three siloxane chains on the basis of the hydrosilyl groupin which u, v and w in the following formula had about the same value,judging from the fact that molecular weights obtained form the GPC dataand H (ppm) were about thrice as much as those in Example 8 (the numberof siloxane chains on the basis of hydrosilyl group was 1) in which thesame conditions as in this example were repeated on the identical scalewith the exception that the kind of chlorosilane was only changed.##STR23##

IR (KBr): 2970 cm⁻¹ (C-H) 2250 cm⁻¹ (Si-H) 1260 cm⁻¹ (Si-CH₃) 1250-1150cm⁻¹ (CF₂, CF₃) 1120-1050 cm⁻¹ (Si-O)

Molecular weight in terms of polystyrene by the use of GPC (toluene):

    ______________________________________                                        Number average molecular weight (Mn)                                                                 33790                                                  Weight average molecular weight (Mw)                                                                 37710                                                  Dispersity (Mw/Mn)     1.1                                                    Quantitative data of Si--H group:                                             H (ppm)                33.8     (ppm)                                         Molecular weight calculated on H (ppm)                                                               29590                                                  Viscosity (25° C.):                                                    681 centipoise                                                                ______________________________________                                    

What is claimed is:
 1. A process for preparing a siloxane compoundrepresented by said general formula (IV) ##STR24## wherein j is aninteger of 1 to 2000, R is an alkyl group having 1 to 4 carbon atoms,and R¹ is a pentafluorophenyl group or a substituent which is astraight-chain or a branched fluoro-alkyl group represented by theformula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,which comprises reacting a compound represented by the general formula(I') ##STR25## wherein d is an integer of 1 to 2000 and R¹ is apentafluorophenyl group or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,witha chlorosilane represented by the general formula (VII) ##STR26##wherein R is an alkyl group having 1 to 4 carbon atoms.
 2. A process forpreparing a siloxane compound represented by said general formula (V)##STR27## wherein each of k and l is an integer of 1 to 2000, R is analkyl group having 1 to 4 carbon atoms, and each of R² and R³ is analkyl group having 1 to 4 carbon atoms, a pentafluorophenyl group or asubstituent which is a straight-chain or a branched fluoroalkyl grouprepresented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R² and R³ is a pentafluorophenyl or fluoroalkylgroup,which comprises reacting a compound or a mixture of two or morecompounds represented by said general formula (I') ##STR28## wherein dis an integer of 1 to 2000 and R¹ is a pentafluorophenyl group or asubstituent which is a straight-chain or a branched fluoroalkyl grouprepresented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, or amixture of a compound represented by said general formula (I') and oneor more kinds of compounds represented by the general formula (VIII)##STR29## wherein q is an integer of 1 to 2000 and R⁷ is an alkyl grouphaving 1 to 4 carbon atoms, with a chlorosilane represented by thegeneral formula (IX) ##STR30## wherein c is 2 and R is an alkyl grouphaving 1 to 4 carbon atoms.
 3. A process for preparing a siloxanecompound represented by said general formula (VI) ##STR31## wherein eachof m, n and p is an integer of 1 to 2000, and a substituent representedby each of R⁴, R⁵ and R⁶ is an alkyl group having 1 to 4 carbon atoms, apentafluorophenyl group, or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R⁴, R⁵ and R⁶ is a pentafluorophenyl or fluoroalkylgroup,which comprises reacting a compound or a mixture of two or morecompounds represented by said general formula (I') ##STR32## wherein dis an integer of 1 to 2000 and R¹ is a pentafluorophenyl group or asubstituent which is a straight-chain or a branched fluoroalky grouprepresented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, or amixture of a compound represented by said general formula (I') and oneor more kinds of compounds represented by the general formula (VIII)##STR33## wherein q is an integer of 1 to 2000 and R⁷ is an alkyl grouphaving 1 to 4 carbon atoms, with a chlorosilane represented by thegeneral formula

    HSiCl.sub.3.


4. A process for preparing a siloxane compound represented by saidgeneral formula (IV) ##STR34## wherein j is an integer of 1 to 2000, Ris an alkyl group having 1 to 4 carbon atoms, and R¹ is apentafluorophenyl group or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,whichcomprises anion polymerizing hexamethylcyclotrisiloxane with one kind ora mixture of two or more kinds of trialkylsilanols represented by thegeneral formula (III) ##STR35## wherein R¹ is a pentafluorophenyl groupor a substituent which is a straight-chain or a branched fluoroalkylgroup represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, or amixture of said trialkylsilanol represented by said general formula(III) and one or more kinds of trialkylsilanols represented by thegeneral formula (X) ##STR36## wherein R⁸ is an alkyl group having 1 to 4carbon atoms, as an initiator in the presence of a lithium catalyst inan amount of 0.05 to 50 mole % based on said initiator in a polarsolvent having no active hydrogen; and then terminating the chain of theresulting polymer with a chlorosilane represented by the general formula(IX) ##STR37## wherein g is 1 and R is an alkyl group having 1 to 4carbon atoms.
 5. A process for preparing a siloxane compound representedby said general formula (V) ##STR38## wherein each of k an dl is aninteger of 1 to 2000, R is an alkyl group having 1 to 4 carbon atoms,and each of R² and R³ is an alkyl group having 1 to 4 carbon atoms, apentafluorophenyl group or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R² and R³ is a pentafluorophenyl or fluoroalkylgroup,which comprises anion polymerizing hexamethylcyclotrisiloxane withone kind or a mixture of two or more kinds of trialkylsilanolsrepresented by general formula (III) ##STR39## wherein R¹ is apentafluorophenyl group or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula II

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, or amixture of said trialkylsilanol represented by said general formula(III) an done or more kinds of trialkylsilanols represented by thegeneral formula (X) ##STR40## wherein R⁸ is an alkyl group having 1 to 4carbon atoms, as an initiator in the presence of a lithium catalyst inan amount of 0.05 to 50 mole % based on said initiator in a polarsolvent having no active hydrogen; and then terminating the chain of theresulting polymer with a chlorosilane represented by the general formula(IX) ##STR41## wherein g is 2 and R is an alkyl group having 1 to 4carbon atoms.
 6. A process for preparing a siloxane compound representedby said general formula (VI) ##STR42## wherein each of m, n and p is aninteger of 1 to 20-00, and a substituent represented by each of R⁴, R⁵and R⁶ is an alkyl group having 1 to 4 carbon atoms, a pentafluorophenylgroup, or a substituent which is a straight-chain or a branchedfluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, andat least one of R⁴, R⁵ and R⁶ is a pentafluorophenyl or fluoroalkylgroup, which comprises anion polymerizing hexamethylcyclotrisiloxanewith one kind or a mixture of two or more kinds of trialkylsilanolsrepresented by the general formula (III) ##STR43## wherein R¹ is apentafluorophenyl group or a substituent which is a straight-chain or abranched fluoroalkyl group represented by the formula II

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a, or amixture of said trialkylsilanol represented by said general formula(III) and one or more kinds of trialkylsilanols represented by thegeneral formula (X) ##STR44## wherein R⁸ is an alkyl group having 1 to 4carbon atoms, as an initiator in the presence of a lithium catalyst inan amount of 0.05 to 50 mole % based on said initiator in a polarsolvent having no active hydrogen; and then terminating the chain of theresulting polymer with a chlorosilane represented by the general formula

    HSiCl.sub.3.


7. A process for preparing a siloxane compound according to claim 4wherein said lithium catalyst is metallic lithium, butyl lithium,lithium hydroxide, a lithium trialkylsilanolate represented by thegeneral formula (XI) ##STR45## wherein each of R⁹, R¹⁰ and R¹¹ is analkyl group having 1 to 4 carbon atoms, a phenyl group, apentafluorophenyl group, or a straight-chain or a branched fluoroalkylgroup represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,or amixture of two or more thereof.
 8. A process for preparing a siloxanecompound according to claim 5 wherein said lithium catalyst is metalliclithium, butyl lithium, lithium hydroxide, a lithium trialkylsilanolaterepresented by the general formula (XI) ##STR46## wherein each of R⁹,R¹⁰ and R¹¹ is an alkyl group having 1 to 4 carbon atoms, a phenylgroup, a pentafluorophenyl group, or a straight-chain or a branchedfluoroalkyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,or amixture of two or more thereof.
 9. A process for preparing siloxanecompound according to claim 6 wherein said lithium catalyst is metalliclithium, butyl lithium, lithium hydroxide, a lithium trialkylsilanolaterepresented by the general formula (XI) ##STR47## wherein each of R⁹,R¹⁰ and R¹¹ is an alkyl group having 1 to 4 carbon atoms, a phenylgroup, a pentafluorophenyl group, or a straight-chain or a branchedfluoroalklyl group represented by the formula (II)

    C.sub.a H.sub.b F.sub.2a-b+1                               (II)

wherein a is an integer of 3 to 18, and b is an integer of 0 to 2a,or amixture of two or more thereof.
 10. A process for preparing a siloxanecompound according to claim 5 wherein the amount of said lithiumcatalyst is in the range of 0.05 to 10 mole % based on saidtrialkylsilanol which is said polymerization initiator.
 11. A processfor preparing a siloxane compound according to claim 6 wherein theamount of said lithium catalyst is in the range of 0.05 to 10 mole %based on said trialkylsilanol which is said polymerization initiator.12. A process for preparing a siloxane compound according to claim 7wherein the amount of said lithium catalyst is in the range of 0.05 to10 mole % based on said trialkylsilanol which is said polymerizationinitiator.
 13. A process for preparing a siloxane compound according toclaim 8 wherein the amount of said lithium catalyst is in the range of0.05 to 10 mole % based on said trialkylsilanol which is saidpolymerization initiator.
 14. A process for preparing a siloxanecompound according to claim 9 wherein the amount of said lithiumcatalyst is in the range of 0.05 to 10 mole % based on saidtrialkylsilanol which is said polymerization initiator.
 15. A processfor preparing a siloxane compound according to claim 5 wherein saidpolar solvent having no active hydrogen is tetrahydrofuran, 1,4-dioxane,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,dimethylformamide, dimethyl sulfoxide or a mixture of two or morethereof.
 16. A process for preparing a siloxane compound according toclaim 6 wherein said polar solvent having no active hydrogen istetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethyleneglycol dimethyl ether, dimethylformamide, dimethyl sulfoxide or amixture of two or more thereof.
 17. A process for preparing a siloxanecompound according to claim 7 wherein said polar solvent having noactive hydrogen is tetrahydrofuran, 1,4-dioxane, ethylene glycoldimethyl ether, diethylene glycol dimethyl ether, dimethylformamide,dimethyl sulfoxide or a mixture of two or more thereof.
 18. A processfor preparing a siloxane compound according to claim 8 wherein saidpolar solvent having no active hydrogen is tetrahydrofuran, 1,4-dioxane,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,dimethylformamide, diemethyl sulfoxide or a mixture of two or morethereof.
 19. A process for preparing a siloxane compound according toclaim 9 wherein said polar solvent having no active hydrogen istetrahydrofuran 1,4-dioxane, ethylene glycol dimethyl ether, diethyleneglycol dimethyl ether, dimethylformamide, dimethyl sulfoxide or amixture of two or more thereof.
 20. A process for preparing a siloxanecompound according to claim 1 wherein said substituent represented by R¹in said general formula (I') comprises a 3,3,3-trifluoropropyl group.21. A process for preparing a siloxane compound according to claim 1wherein said substituent represented by R¹ in said general formula (I')comprises a tridecafluoro-1,1,2,2-tetrahydrooctyl group.
 22. A processfor preparing a siloxane compound according to claim 1 wherein saidsubstituent represented by R¹ in said general formula (I') comprises aheptadecafluoro -1,1,2,2-tetrahydrodecyl group.
 23. A process forpreparing a siloxane compound according to claim 2 wherein saidsubstituent represented by at least one of R² and R³ in said generalformula (V) comprises a 3,3,3-trifluoropropyl group.
 24. A process forpreparing a siloxane compound according to claim 2 wherein saidsubstituent represented by at least one of R² or R³ in said generalformula (V) comprises a tridecafluoro-1,1,2,2-tetrahydrooctyl group. 25.A process of preparing a siloxane compound according to claim 2 whereinsaid substituent represented by at least one of R² or R³ in said generalformula (V) comprises a heptadecafluoro -1,1,2,2-tetrahydrodecyl group.26. A process for preparing a siloxane compound according to claim 3wherein said substituent represented by at least one of R⁴, R⁵ and R⁶ insaid general formula (VI) comprises a 3,3,3-trifluoropropyl group.
 27. Aprocess for preparing a siloxane compound according to claim 3 whereinsaid substituent represented by at least one of R⁴, R⁵ and R⁶ in saidgeneral formula (VI) comprises a tridecafluoro-1,1,2,2-tetrahydrooctylgroup.
 28. A process for preparing a siloxane compound according toclaim 3 wherein said substituent represented by at least one of R⁴, R⁵and R⁶ and in said general formula (VI) comprises a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.
 29. A siloxane compound represented bythe general formula (IV) ##STR48## wherein j is an integer of 1 to 2000,R is an alkyl group having 1 to 4 carbon atoms, and R¹ is apentafluorophenyl group or a tridecafluoro-1,1,2,2-tetrahydrooctyl groupor a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.
 30. A siloxanecompound represented by the general formula (V) ##STR49## wherein eachof k and l is an integer of 1 to 2000, R is an alkyl group having 1 to 4carbon atoms, and each of R² and R³ is an alkyl group having 1 to 4carbon atoms, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, aheptadecafluoro-1,1,2,2-tetrahydrodecyl group on pentafluorophenyl groupand at least one of R² and R³ is a tridecafluoro-1,1,2,2-tetrahydrooctylgroup, a heptadecafluoro-1,1,2,2-tetrahyrodecyl group orpentafluorophenyl group.
 31. A siloxane compound represented by thegeneral formula (VI) ##STR50## wherein each of m, n and p is an integerof 1 to 2000, and a substituent represented by each of R⁴, R⁵ and R⁶ isan alkyl group having 1 to 4 carbon atoms, atridecafluoro-1,1,2,2-tetrahydrooctyl group, aheptadecafluoro-1,1,2,2-tetrahydrodecyl group or a pentafluorophenylgroup and at least one of R⁴, R⁵ and R⁶ is atridecafluoro-1,1,2,2-tetrahydrooctyl group, aheptadecafluoro-1,1,2,2-tetrahydrodecyl group or pentafluorophenylgroup.
 32. A siloxane compound according to claim 29 wherein saidsubstituent represented by R' in said general formula (I) comprises atridecafluoro 1,1,2,2-tetrahydrooctyl group.
 33. A siloxane compoundaccording to claim 29 wherein said substituent represented R' in saidgeneral formula (IV) comprises a heptadecafluoro-1,1,2,2-tetrahydrodecyl group.
 34. A siloxane compound according toclaim 30 wherein each of R² and R³ represented in said general formula Vcomprises a tridecafluoro-1,1,2,2-tetrahydrooctyl group.
 35. A siloxanecompound according to claim 30 wherein each of R² and R³ represented insaid general formula V comprises aheptadecafluoro-1,1,2,2-tetrahydrodecyl group.
 36. A siloxane compoundaccording to claim 31 wherein each of R⁴, R⁵, and R⁶ represented in saidgeneral formula VI comprises a tridecafluoro-1,1,2,2-tetrahydrooctylgroup.
 37. A siloxane compound according to claim 31 wherein each of R⁴,R⁵, and R⁶ represented in said general formula VI comprises aheptadecafluoro-1,1,2,2-tetrahydrodecyl group.